CN105393341B - Film formation composition and its film and the manufacture method using its organic semiconductor device - Google Patents

Film formation composition and its film and the manufacture method using its organic semiconductor device Download PDF

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CN105393341B
CN105393341B CN201480041085.6A CN201480041085A CN105393341B CN 105393341 B CN105393341 B CN 105393341B CN 201480041085 A CN201480041085 A CN 201480041085A CN 105393341 B CN105393341 B CN 105393341B
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fluorine
film
fluororesin
organic semiconductor
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CN105393341A (en
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照井贵阳
小森谷治彦
小林史人
原由香里
原育成
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Central Glass Co Ltd
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Central Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/236—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers using printing techniques, e.g. applying the etch liquid using an ink jet printer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene

Abstract

The film formation of the present invention is included with composition：The fluororesin and fluorine series solvent of the repeat unit represented containing formula (1).(R1It is each independently hydrogen atom, fluorine atom, methyl or trifluoromethyl.R2It is each independently the fluorine-containing alkyl of the ring-type of the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15, the hydrogen atom in alkyl can be replaced by fluorine atoms, and at least one fluorine atom is included in repeat unit.) said composition can form film on organic semiconductor film, when the exquisite pattern of organic semi-conductor is obtained in photoetching process etc., there is patience to etching solvent, be useful in the manufacture method of organic semiconductor device.

Description

Film formation composition and its film and the system using its organic semiconductor device Make method
Technical field
The present invention relates to on organic semiconductor film carry out coating film forming film formation composition and its film and Use the manufacture method of its organic semiconductor device.
Background technology
Organic semiconductor is the organic matter for the property for showing semiconductor, it is known to which pentacene, anthracene, aphthacene, phthalocyanine etc. have The polyhenylene system such as machine low molecule, polyacetylene system electroconductive polymer, polyparaphenylene and its derivative, polyphenylacetylene and its derivative The heterocycle system such as electroconductive polymer, polypyrrole and its derivative, polythiophene and its derivative, poly- Furan and its derivatives electric conductivity The organic semiconductors such as macromolecule, Polyaniline and its derivative isoiony electroconductive polymer, organic charge movement complex compound etc.. Especially, organic low molecular semiconductor, polythiophene etc. be capable of the organic semiconductor of wet can also be in organic polymer substrate Deng film forming on organic matrix, if forming circuit on the organic semiconductor film being formed on organic material, tool can be manufactured There is organic electrochromic display of bendability etc..
In the manufacture of semiconductor element, entering to be about to semiconductor film microfabrication, (hereinafter sometimes referred to pattern is processed.) Into the operation of desired semiconductor circuit, and it is provided for protecting semiconductor film and fine for protecting in microfabrication The film of circuit pattern after processing.
Typically for semiconductor circuit, using photoetching process, by exposed and developed against corrosion on semiconductor film to being coated on Agent film is patterned, and then carries out pattern processing to semiconductor film by dry-etching or Wet-type etching, and the photoetching process is The real estate exposure that photosensitive material (resist) is coated with across photomask or mask etc. is pattern, is formed by being exposed The technology for the pattern that position and the position not being exposed are formed.
In the manufacture of organic semiconductor device, not using only photoetching process, also use and utilize relief printing plate, intaglio plate, lithographic plate or silk screen Deng print process, especially by the minute asperities being engraved on mould press on the film being coated on substrate and the technology transferred That is stamped method, after mould pattern is transferred on film, organic semiconductor film is etched, carries out pattern processing.
When carrying out pattern processing to organic semiconductor film using Wet-type etching, formed on organic semiconductor film for protecting Film of the organic semiconductor film from the etchant influence as stripping solvent.As the film formation composition for forming film Required condition, two important conditions can be included.1st condition is can be dissolved in that organic semiconductor film will not be made molten Solution and swelling solvent in and the wet type film forming on organic semiconductor film.2nd condition is to carry out pattern to organic semiconductor film During processing, film obtained from foregoing wet type film forming can protect organic semiconductor film and so that etching will not involve to coated organic Semiconductor.However, it is difficult to met the film formation composition of the two conditions simultaneously.
The dry-etching and the Wet-type etching using solvent of the plasma irradiating for being etched with utilizing in vacuum plant etc., but Organic semiconductor film dissolves in etchant, therefore Wet-type etching is easy.Generally, organic semiconductor contains fragrant ring group in the structure Group or heterocyclic group, therefore it is soluble in the fragrant family solvent such as benzene, toluene or dimethylbenzene.
Patent document 1 and patent document 2 discloses that being etched to organic semiconductor film and semiconductor circuit pattern being made When be not etched by the excellent film formation composition and its film of anti-corrosion etchant of agent erosion.
Organic lead patent document 1 discloses the manufacture method of the organic semiconductor device of the excellent in stability of electrical characteristics and partly Volume elements part, as the material for forming film when manufacturing organic semiconductor device on organic semiconductor film, using containing selected from carbonic acid Sub- propyl ester, acetonitrile, dimethyl sulfoxide (DMSO) at least one kind of organic solvent and dissolve in the film of organic compound of organic solvent and formed Liquid.
Patent document 2 discloses that photoreactivity is high and can pattern and can form hydrophobicity height and dielectric property The photosensitive polymer combination and its film and pattern formation method of excellent envelope, as the molten of photosensitive polymer combination Agent, such as alcohols, hydro carbons, halogenated hydrocarbons, ethers, esters, ketone, dioxane, carbitol class, glycol ether-ether can be included Class, amide-type, sulfoxide type or nitrile etc..
It is however, organic molten for being used in the material that film is formed on organic semiconductor film described in patent document 1 For the solvent used in photosensitive polymer combination described in agent, patent document 2, it is difficult to which asserting must will not be to organic Semiconductor film impacts.So, it is desirable to have concurrently can coating film forming without immerse organic semiconductor film, photoetching can be passed through Method or stamped method etc. carry out the film formation composition and its film of pattern processing.
In addition, patent document 3 discloses that a kind of eurymeric anti-corrosion agent composition of laser for vacuum ultraviolet region, it contains Play the role of by sour acrylic resin and acid agent to make the dissolubility to alkaline aqueous solution change, wherein, contain There is the acrylic resin for including following polymer, the polymer includes third using the group with fluorine atom as esteratic site Olefin(e) acid ester or methacrylate unit.
Patent document 4 discloses that a kind of eurymeric for more than 1nm and the laser of below 190nm vacuum ultraviolet region resists Lose agent composition, its contain by the effect of acid and make acrylic resin that the dissolubility to alkaline aqueous solution changes and Acid agent, wherein, use the acrylic resin for the unit being polymerized with methacrylate.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-74616 publications
Patent document 2：Japanese Unexamined Patent Publication 2011-180269 publications
Patent document 3：Japanese Unexamined Patent Publication 2001-154362 publications
Patent document 4：Japanese Unexamined Patent Publication 2005-99856 publications
The content of the invention
Problems to be solved by the invention
It is an object of the present invention to provide can on organic semiconductor film by film coating film forming without immersing organic half Electrically conductive film, pattern processing can be carried out by photoetching process or stamped method etc., Wet-type etching and pattern are carried out to organic semiconductor film The agent film immersed and the film formation composition wherein used will not be etched when being processed into semiconductor circuit and uses the film The manufacture method of organic semiconductor device.
The solution used to solve the problem
The present inventor etc. has made intensive studies, and as a result finds, the solvent phase recorded with patent document 1 or patent document 2 Than the influence of dissolving and the swelling of the fluorine series solvent such as hydrofluorocarbons or fluorine-containing ether to being capable of the organic semiconductor film of wet etc. It is few.It is solvable and to organic semiconductor to fluorine series solvents such as hydrofluorocarbons or fluorine-containing ethers to have been sought based on the opinion, the present inventor etc. Film is etched and the fluororesin of agent immersion will not be etched when carrying out pattern processing.As a result, it is found that for organic half The fluororesin of fluororesin film and the fluorine series solvent for being dissolved are formed on electrically conductive film, has obtained including these fluororesin and fluorine The film formation composition of series solvent, so as to complete the present invention.
Manufacture method of the invention for its organic semiconductor device of film formation composition and its film and use, institute Stating film formation composition influences minimum fluorine series solvent using the dissolving on organic semiconductor film or swelling etc., makes to the fluorine system Solvent obtains for the specific fluororesin dissolving that can dissolve and anti-corrosion etchant is excellent, for being formed on organic semiconductor film Fluororesin film.If using the film formation composition of the present invention, wet can be carried out without being immersed in inorganic substrate Or the organic semiconductor film and organic polymer substrate formed on organic polymer substrate, it can be formed on organic semiconductor film Fluororesin film.The fluororesin film can be patterned by photoetching, printing, such as stamped method, it is difficult to which be dissolved in has to lower floor Hydrocarbon system solvent or fragrant family solvent that machine semiconductor film uses when being etched, the etchant such as benzene, toluene or dimethylbenzene, The patterning of organic semiconductor film can be carried out, can apply to the manufacture method of organic semiconductor device.
That is, the present invention includes following technical schemes 1~23.
[technical scheme 1]
A kind of film formation composition, it is the film formation combination for forming fluororesin film on organic semiconductor film Thing, it is included：The fluororesin and fluorine series solvent of the repeat unit represented containing formula (1).
(in formula, R1It is each independently hydrogen atom, fluorine atom, methyl or trifluoromethyl, R2Be each independently carbon number 1~ The fluorine-containing alkyl of the ring-type of 15 straight-chain, the branched of carbon number 3~15 or carbon number 3~15, hydrogen atom in alkyl can be by Fluorine atom substitutes, and at least one fluorine atom is included in repeat unit.)
[technical scheme 2]
The film formation composition of technical scheme 1, wherein, fluorine series solvent contains hydrofluorocarbons or fluorine-containing ether.
[technical scheme 3]
The film formation composition of technical scheme 2, wherein, fluorine series solvent contain the straight-chain of carbon number 4~8, branched or The hydrofluorocarbons that at least one of hydrogen atom in the hydrocarbon and hydrocarbon of ring-type is replaced by fluorine atoms are as hydrofluorocarbons.
[technical scheme 4]
The film formation composition of technical scheme 2, wherein, the fluorine-containing ether that fluorine series solvent contains formula (2) expression, which is used as, to be contained Fluorine ether.
R3-O-R4 (2)
(in formula, R3And R4It is each independently the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15 Ring-type alkyl, at least one of the hydrogen atom in compound is replaced by fluorine atoms.)
[technical scheme 5]
The film formation composition of technical scheme 1~4, wherein, the fluorine-containing alcohol that fluorine series solvent also represents containing formula (3),
R5-OH (3)
(in formula, R5For the alkyl of the ring-type of the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15, At least one of hydrogen atom in alkyl is replaced by fluorine atoms.)
[technical scheme 6]
The film formation composition of technical scheme 1~5, it is more than 30 mass % and below 65 mass % that it, which contains fluorine-containing rate, Fluororesin as fluororesin.
[technical scheme 7]
The film formation composition of technical scheme 1~6, it is more than 50 mass % and below 80 mass % that it, which contains fluorine-containing rate, Fluorine series solvent as fluorine series solvent.
[technical scheme 8]
A kind of fluororesin film, its be the film formation of technical scheme 1~7 is coated on organic semiconductor film with composition and Formed.
[technical scheme 9]
A kind of manufacture method of organic semiconductor device, it includes following process：The film of technical scheme 1~7 is formed It is coated on composition on organic semiconductor film and forms the process of fluororesin film, the work of pattern processing is carried out to the fluororesin film Sequence and the process for carrying out pattern processing to organic semiconductor film by etching.
[technical scheme 10]
The manufacture method of technical scheme 9, wherein, use photoetching process in the process for carrying out pattern processing to fluororesin film.
[technical scheme 11]
The manufacture method of technical scheme 9, wherein, use print process in the process for carrying out pattern processing to fluororesin film.
[technical scheme 12]
The manufacture method of technical scheme 9.Wherein, stamped method is used in the process for carrying out pattern processing to fluororesin film.
[technical scheme 13]
The manufacture method of technical scheme 9~12, wherein, by etching the process that pattern processing is carried out to organic semiconductor film It is the process for carrying out pattern processing to organic semiconductor film by using the Wet-type etching of hydrocarbon system solvent or fragrant family solvent.
[technical scheme 14]
The manufacture method of technical scheme 13, wherein, fragrant family solvent is benzene, toluene or dimethylbenzene.
[technical scheme 15]
The manufacture method of 9~technical scheme of technical scheme 14, it includes the process for removing fluororesin film.
[technical scheme 16]
The manufacture method of technical scheme 15, wherein, the process that fluororesin film is removed is fluororesin film is dissolved into fluorine system Process in solvent.
[technical scheme 17]
The manufacture method of technical scheme 16, wherein, fluorine series solvent contains hydrofluorocarbons or fluorine-containing ether.
[technical scheme 18]
The manufacture method of technical scheme 17, wherein, fluorine series solvent contains the straight-chain of carbon number 4~8, branched or ring-type The hydrofluorocarbons that at least one of hydrogen atom in hydrocarbon and hydrocarbon is replaced by fluorine atoms are as hydrofluorocarbons.
[technical scheme 19]
The manufacture method of technical scheme 17, wherein, fluorine series solvent contains the fluorine-containing ether of formula (2) expression as fluorine-containing ether.
R3-O-R4 (2)
(in formula, R3And R4It is each independently the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15 Ring-type alkyl, at least one of the hydrogen atom in compound is replaced by fluorine atoms.)
[technical scheme 20]
The manufacture method of technical scheme 16~19, wherein, the fluorine-containing alcohol that fluorine series solvent also represents containing formula (3).
R5-OH (3)
(in formula, R5For the alkyl of the ring-type of the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15, At least one of hydrogen atom in alkyl is replaced by fluorine atoms.)
[technical scheme 21]
A kind of organic semiconductor device, it is manufactured by the manufacture method of technical scheme 9~20.
[technical scheme 22]
A kind of display of organic electroluminescence, it use the organic semiconductor device of technical scheme 21.
[technical scheme 23]
A kind of liquid crystal display, it use the organic semiconductor device of technical scheme 21.
For the film formation composition of the present invention, when being coated with organic semiconductor film, organic semiconductor will not be made Film dissolves or is swelled and immerses, therefore can carry out wet type film forming on organic semiconductor film and form film.And the fluororesin Film, can when carrying out pattern processing using photoetching process, printing or impressing and then carrying out Wet-type etching to organic semiconductor film Pattern processing is not carried out with immersing to organic semiconductor film by the etchant such as hydrocarbon system solvent or fragrant family solvent.
Fluorine series solvent contained by the film formation composition of the present invention will not make to have when being coated on organic semiconductor film Machine semiconductor film dissolves or is swelled and immerses, therefore can carry out the wet of fluororesin film on the organic material.And the film , can not when carrying out pattern processing using photoetching process, printing, such as stamped method, carrying out Wet-type etching to organic semiconductor film Pattern processing is carried out with immersing to organic semiconductor film by the etchant such as hydrocarbon system solvent or fragrant family solvent.
So, if using film formation composition of the invention, the organic semiconductor film on substrate can be carried out micro- Fining-off, circuit pattern is made, the manufacture of organic semiconductor device can be suitably used for.
Brief description of the drawings
Fig. 1 is an example for illustrating the organic semi-conductor manufacture method for having used film formation composition Figure.(A) be on substrate formed organic semiconductor film figure.(B) be on organic semiconductor film formed fluororesin film figure. (C) it is that the figure that pattern is formed has been carried out to fluororesin film.(D) be to organic semiconductor film carry out Wet-type etching figure.(E) be by The figure that fluororesin film is peeled off.
Embodiment
Hereinafter, the film formation to the present invention is said with composition and using its organic semi-conductor manufacture method It is bright.
The film formation of the present invention is also contained in addition to the fluororesin containing film formation with composition and is used for solution The fluorine series solvent that form is coated.
1. fluororesin
The fluororesin that the film formation of the present invention is included with composition contains the repeat unit of formula (1) expression.
(in formula, R1It is each independently hydrogen atom, fluorine atom, methyl or trifluoromethyl, R2Be each independently carbon number 1~ The alkyl of the ring-type of 15 straight-chain, the branched of carbon number 3~15 or carbon number 3~15, the hydrogen atom in alkyl can be former by fluorine Son substitutes, and at least one fluorine atom is included in repeat unit.)
By making repeat unit (1) include fluorine atom, the fluororesin has the compatibility with fluorine series solvent, and repeats single First (1) adjacently has the ester bond as polar group with main chain, therefore the fluororesin film that fluororesin-coated film forming is obtained is rich There is flexibility, flat and flawless fluororesin film can be obtained.And then due to having the alkyl being fluorinated in side chain, therefore Dissolubility of the fluororesin in fluorine series solvent is excellent, and excellent to the patience of etching solvent.
It should be noted that from the point of view of the easy degree of monomer synthesis, preferably R2For the straight-chain of carbon number 2~14, carbon number 3 The material that at least one of hydrogen atom in the alkyl and alkyl of~6 branched is replaced by fluorine atoms.
R2Specifically during the group of straight-chain, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptan can be exemplified Base, octyl group, the straight-chain alkyl of nonyl or carbon number 10~14.In R2In, with the carbon original being bonded directly to beyond the carbon atom of oxygen The hydrogen atom that sub-key is closed can be replaced by fluorine atoms.
R2For straight-chain group when, group that preferably following formulas (4) represent.
(X is hydrogen atom or fluorine atom, and n is 1~4 integer, and m is 1~14 integer.)
From the point of view of the easy degree of monomer synthesis, n is preferably 1~2 integer.
In addition, R2Specifically during the group of branched, 1,1,1,3,3,3- hexafluoro isopropyl, 1- (three can be exemplified Methyl fluoride) five fluoropropyls of -2,2,3,3,3-, double (the trifluoromethyl) -2,2,2- trifluoroethyls of 1,1- or 1,1- it is double (trifluoromethyl) Ethyl.
The fluororesin that the film formation of the present invention is included with composition contains a kind or 2 kinds of the repeat unit of formula (1) expression More than.In addition, the repeat unit of the structure beyond formula (1) represents can also be included.
The fluororesin that is included with composition of film formation of the present invention for example can be by the structure that represents following formulas (5) Acrylate derivative polymerize as monomer and obtained.
(in formula, R1、R2It is identical with formula (1).)
The acrylate derivative that may be used as monomer is the compound that formula (5) represents.
In formula (5), R2For branched when, such as can exemplify it is following shown in, respectively by 1,1,1,3,3,3- hexafluoro Propane -2- alcohol (molecular formula：CF3CH(OH)CF3), 1,1,1,3,3,4,4,4- octafluorobutane -2- alcohol (molecular formula：CF3CH(OH) CF2CF3), 2- Trifluoromethyl-1s, 1,1,3,3,3- HFC-236fa -2- alcohol (molecular formula：(CF3)3) or 2- Trifluoromethyl-1s, COH 1,1- trifluoro propane -2- alcohol (molecular formula：(CF3)2(CH3) COH) derive obtained acrylate, methacrylate, α-fluorine first Base acrylate or α-trifluoromethyl acrylate ester it is preferable to use.
In formula (5), R2For straight-chain when, as concrete example, the monomer of following formulas (6) expression can be exemplified.
(in formula, R6For hydrogen atom, fluorine atom, methyl or trifluoromethyl, R7For hydrogen atom or fluorine atom, n be 1~4 it is whole Number, m are 1~14 integer.)
In formula (6), from the point of view of the easy degree of monomer synthesis, n is preferably 1~3 integer, m be preferably 1~14 it is whole Number.
In formula (6), from the point of view of the easy degree of monomer synthesis, R6Preferably hydrogen atom or methyl.
The fluorine-containing rate for the fluororesin that these monomers are polymerized relative to the gross mass of fluororesin for more than 30 mass % and Below 65 mass %, more preferably more than 40 mass % and below 55 mass %.It is easily molten if if fluorine-containing rate is within the range Solution is in fluorine series solvent.
The molecular weight of fluororesin that the film formation of the present invention is included with composition with Weight-average molecular gauge be preferably 2,000 with It is upper and less than 200,000, more preferably more than 3,000 and less than 15,000.To the patience of etching solvent when molecular weight is smaller Deficiency, molecular weight is than its dissolubility deficiency when big in fluorine series solvent, it is difficult to forms fluororesin film by coating.
In the monomer that aforementioned formula (6) represents, R6、R7, n and m preferably using the combination shown in table 1 below~3, especially No.2~9 shown in further preferred table 1 below, 11,12,15,16,19, the No.40 shown in table 2 below, 43,44,47~55,57, 58 and table 3 below shown in No.85,88,91,92,94~103,105.
[table 1]
<The example of repeat unit>
No. n m R6 R7
1 1 1 F H
2 1 1 CF3 H
3 1 1 CH3 F
4 1 1 H F
5 1 1 F F
6 1 1 CF3 F
7 1 2 CH3 H
8 1 2 H H
9 1 2 F H
10 1 2 CF3 H
11 1 2 CH3 F
12 1 2 H F
13 1 2 F F
14 1 2 CF3 F
15 1 4 CH3 H
16 1 4 H H
17 1 4 F H
18 1 4 CF3 H
19 1 4 CH3 F
20 1 4 H F
21 1 4 F F
22 1 4 CF3 F
23 1 6 CH3 H
24 1 6 H H
25 1 6 F H
26 1 6 CF3 H
27 1 6 CH3 F
28 1 6 H F
29 1 6 F F
30 1 6 CF3 F
31 1 8 CH3 H
32 1 8 H H
33 1 8 F H
34 1 8 CH3 F
35 1 8 H F
36 1 10 CH3 H
37 1 10 H H
38 1 10 CH3 F
[table 2]
No. n m R6 R7
39 2 1 F H
40 2 1 CF3 H
41 2 1 CH3 F
42 2 1 H F
43 2 1 F F
44 2 1 CF3 F
45 2 2 CH3 H
46 2 2 H H
47 2 2 F H
48 2 2 CF3 H
49 2 2 CH3 F
50 2 2 H F
51 2 2 F F
52 2 2 CF3 F
53 2 4 CH3 H
54 2 4 H H
55 2 4 F H
56 2 4 CF3 H
57 2 4 CH3 F
58 2 4 H F
59 2 4 F F
60 2 4 CF3 F
61 2 6 CH3 H
62 2 6 H H
63 2 6 F H
64 2 6 CF3 H
65 2 6 CH3 F
66 2 6 H F
67 2 6 F F
68 2 6 CF3 F
69 2 8 CH3 H
70 2 8 H H
71 2 8 F H
72 2 8 CF3 H
73 2 8 CH3 F
74 2 8 H F
75 2 8 F F
76 2 8 CF3 F
77 2 10 CH3 H
78 2 10 H H
79 2 10 F H
80 2 10 CH3 F
81 2 10 H F
82 2 12 CH3 H
83 2 12 CH3 F
[table 3]
No. n m R6 R7
84 3 1 F H
85 3 1 CF3 H
86 3 1 H F
87 3 1 F F
88 3 1 CF3 F
89 3 2 CH3 H
90 3 2 H H
91 3 2 F H
92 3 2 CF3 H
93 3 2 CH3 F
94 3 2 H F
95 3 2 F F
96 3 2 CF3 F
97 3 4 CH3 H
98 3 4 H H
99 3 4 F H
100 3 4 CF3 H
101 3 4 CH3 F
102 3 4 H F
103 3 4 F F
104 3 4 CF3 F
105 3 6 CH3 H
106 3 6 H H
107 3 6 F H
108 3 6 CF3 H
109 3 6 CH3 F
110 3 6 H F
111 3 6 F F
112 3 6 CF3 F
113 3 8 CH3 H
114 3 8 H H
115 3 8 F H
116 3 8 CF3 H
117 3 8 CH3 F
118 3 8 H F
119 3 8 F F
120 3 8 CF3 F
121 3 10 CH3 H
122 3 10 H H
123 3 10 F H
124 3 10 CF3 H
125 3 10 CH3 F
126 3 10 H F
127 3 10 F F
128 3 12 CH3 H
129 3 12 H H
130 3 12 F H
131 3 12 CH3 F
132 3 12 H F
133 3 14 CH3 H
The fluororesin that the film formation of the present invention is included with composition is a kind or 2 kinds of the monomer for representing aforementioned formula (5) Obtained from being polymerize above.
In addition, will not damage in deliquescent scope of the fluororesin relative to fluorine series solvent, can also add in the feed Add the monomer beyond the monomer of aforementioned formula (5) expression.Relative to the gross mass of fluororesin, preferably below 10 mass %.
For example, can exemplify, α positions are substituted or unsubstituted acrylate, alpha-olefin, Fluorine containing olefine or generating vinyl carboxylate Ester.At least one of the hydrogen atom of these monomers can be fluorinated.As acrylate, acrylic acid, metering system can be exemplified Acid, the methyl esters of alpha-fluoro acrylic acid or α-trifluoromethyl acrylate, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, tertiary fourth Ester, pentyl ester, isopentyl ester, own ester, cyclohexyl, cyclohexylmethyl, 2- hydroxy methacrylates, 2- hydroxy propyl esters, 3- hydroxy propyl esters, 4- hydroxyls Cyclohexyl, 4- (hydroxymethyl) cyclohexylmethyl, norbornene ester, isobornyl thiocyanoacetate, norbornyl ester, methoxyl group methyl esters, methoxy acrylate, Ethoxy ethyl ester, ethoxy ethoxyethyl acrylate or methoxyethoxyethyl acrylate.As vinyl carboxylates, vinyl acetate can be included Ester, propionate, vinyl butyrate, vinyl caproate, vinyl laurate, vinyl palmitate, stearic acid vinyl ester, spy Vinyl valerate, vinyl chloroacetate, vinyl methacrylate or vinyl benzoate.
The preferable fluororesin that film formation on the present invention is included with composition, specifically repeat list comprising following The fluororesin of at least any of repeat unit in member.
[polymerization, purification process]
In order that monomer polymerize and obtains the fluororesin that the film formation of the present invention is included with composition, such as one can be used As known radical polymerization, specifically, can use azo-compound, peroxide, persulfate compounds or oxidation also The radical initiators such as former based compound are polymerize as the initiator of radical reaction.
In polymerisation, solvent can also be used in addition to monomer and initiator.As polymer solvent, can use each Kind organic matter, such as the esters such as ethyl acetate, butyl acetate or propylene glycol monomethyl ether, acetone, 2- fourths can be exemplified Ketone either the aromatic hydrocarbon such as ether, benzene or toluene such as the ketone such as cyclohexanone, Di Iso Propyl Ether, dibutyl ethers or tetrahydrofuran, oneself Thing obtained from least one of the hydrogen atom of the hydrocarbon such as alkane, heptane or hexamethylene or these organic solvents is substituted by halogen atom Matter.In addition, it is also used as polymer solvent with the foregoing fluorine series solvent of the solvent of composition as film formation.
Relative to the gross mass of reaction system, monomer concentration during polymerization be preferably more than 1 mass % and 95 mass % with Under, more preferably more than 10 mass % and below 80 mass %.The reactivity of polymerisation when the concentration of monomer is less than the scope Reduce, the viscosity of polymeric solution uprises, manufactures change difficulty when concentration is higher than the scope.
It is desirable that being purified after the reaction, unreacted monomer is reduced.As purification process, can use as follows Method etc.：Distilled using decompression operation or heating remove residual monomer, using poor solvent reprecipitation operation, to polymerization The liquid-liquid cleaning operation of thing solution or by polymer solids stirring and washing in a solvent.These methods can also be applied in combination.
2. fluorine series solvent
The fluorine series solvent that the film formation of the present invention is included with composition is the fluorine series solvent containing hydrofluorocarbons or fluorine-containing ether.
Fluorine series solvent contains at least one of the straight-chain of carbon number 4~8, the hydrocarbon of branched or ring-type and the hydrogen atom in hydrocarbon The hydrofluorocarbons being replaced by fluorine atoms are as hydrofluorocarbons.
In addition, fluorine series solvent is preferably fluorine series solvent of the fluorine-containing ether for containing formula (2) expression as fluorine-containing ether.
R3-O-R4 (2)
(in formula, R3And R4It is each independently the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15 Ring-type alkyl, at least one of the hydrogen atom in compound is replaced by fluorine atoms.)
And then fluorine series solvent can include the fluorine series solvent of the fluorine-containing alcohol also represented containing formula (3).
R5-OH (3)
(in formula, R5For the alkyl of the ring-type of the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15, At least one of hydrogen atom in alkyl is replaced by fluorine atoms.)
The fluorine series solvent that the film formation of the present invention is included with composition is the fluorine series solvent for making foregoing fluororesin dissolving. The Oil repellent of fluorine series solvent is not particularly limited, in order to dissolve rapidly, the gross mass relative to fluorine series solvent is 50 mass % Above and below 70 mass %, more preferably more than 55 mass % and below 70 mass %.During more than 70 mass %, foregoing fluorine tree Fat becomes fully to dissolve.In addition, when being less than 50 mass %, when being coated with or printing on organic semiconductor film, make sometimes The surface dissolving or swelling of organic semiconductor film.The fluorine series solvent that film formation as the present invention is included with composition, can be with excellent Choosing uses hydrofluorocarbons or fluorine-containing ether as shown below.
[fluorine-containing hydrocarbon system solvent]
The ozone destruction coefficient of hydrofluorocarbons is low, and the fluorine series solvent that the film formation as invention is included with composition is preferred 's.Especially, the thing being replaced by fluorine atoms for straight-chain, the hydrocarbon of branched or ring-type and at least one of hydrogen atom of carbon number 4~8 Matter is easily coated with, and is preferable.
As such hydrofluorocarbons, butane, pentane, hexane, heptane, octane, pentamethylene or ring can be specifically exemplified Hydrofluorocarbons obtained from least one of the hydrogen atom of hexane is replaced by fluorine atoms.If particular instantiation, can exemplify for example CH3CF2CH2CF3、CF3CHFCHFCF2CF3、CF3CF2CF2CF2CF2CH2CH2CH3And the hydrofluorocarbons of following formula.
The boiling point of hydrofluorocarbons need it is higher with substrate temperature during composition than coated film formation, it is preferably higher than coating temperature by 20 More than DEG C, further preferably it is high more than 50 DEG C.If the substrate temperature when boiling point of hydrofluorocarbons is less than coated film formation composition, Then hydrofluorocarbons are rapidly volatilized in painting work, and the fluororesin film formed is difficult to obtain sufficient flatness.In addition, used The preferred boiling point of hydrofluorocarbons for less than 200 DEG C, be more preferably less than 180 DEG C.When the boiling point of hydrofluorocarbons is less than 200 DEG C, Evaporative removal in the fluororesin film for forming hydrofluorocarbons with composition from coated film formation easily by heating.
In foregoing hydrofluorocarbons, as the example with particularly preferred boiling point, following material can be exemplified.
CF3CHFCHFCF2CF3(Du Pont-Mitsui Fluorochemicals Co., Ltd. system, Vertrel XF, 55 DEG C of boiling point)
The hydrofluorocarbons (Zeon Corporation systems, ZEORORA H, 83 DEG C of boiling point) of following formula
CF3CF2CF2CF2CF2CH2CH2CH3(Asahi Glass Co., Ltd's system, ASAHIKLIN AC-6000,114 DEG C of boiling point)
It should be noted that Vertrel is molten with the fluorine system of Du Pont-Mitsui Fluorochemicals Co., Ltd.s The trade name of agent, ZEORORA are with Zeon Corporation fluorine series solvent (HFC classes) and ASAHIKLIN with Asahi Glass strain The trade name progress of the fluorine series solvent of formula commercial firm is commercially available, and above-mentioned trade name has carried out trade mark registration respectively.
[fluorine-containing ether]
In addition, from ozone destruction coefficient low, fluorine-containing ether can be used as fluorine series solvent.Particularly preferred use comprising The solvent for the fluorine-containing ether that following formulas (2) represent.
R3-O-R4 (2)
(in formula, R3For the alkyl of the ring-type of the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15, At least one of hydrogen atom in alkyl can be replaced by fluorine atoms.R4For the straight-chain of carbon number 1~15, the side chain of carbon number 3~15 The alkyl of the ring-type of shape or carbon number 3~15, at least one of the hydrogen atom in group can be replaced by fluorine atoms.)
In formula (2), R3With R4The dissolubility of the foregoing fluororesin of the different material of 2 substituents represented is high, is preferred 's.
In formula (2), R3Preferably methyl, ethyl, propyl group, isopropyl, vinyl, pi-allyl or methyl ethylene.This At least one of hydrogen atom in a little alkyl can be replaced by fluorine atoms.
In formula (2), R4Can specifically exemplify methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, The tert-butyl group, 1- amyl groups, 2- amyl groups, 3- amyl groups, 1- hexyls, 2- hexyls, 3- hexyls, 1- heptyl, 2- heptyl, 3- heptyl, 1- octyl groups, 2- octyl groups, 3- octyl groups, 1- nonyls, 2- nonyls, 1- decyls, 2- decyls, undecyl, dodecyl, cyclopenta, cyclohexyl, ring Phenyl-methyl or cyclohexyl methyl.At least one of hydrogen atom in these alkyl is replaced by fluorine atoms.In addition, these alkyl There can be unsaturated bond.
The boiling point of fluorine-containing ether need it is higher with substrate temperature during composition than coated film formation, it is preferably higher than coating temperature More than 20 DEG C, more preferably it is high more than 50 DEG C.Substrate when if the boiling point of fluorine-containing ether is less than coated film formation composition Temperature, then fluorine-containing fatty ether rapidly volatilizees in painting work, and the fluororesin film formed is difficult to obtain sufficient flatness. In addition, the used preferred boiling point of fluorine-containing ether is less than 200 DEG C, more preferably less than 180 DEG C.The boiling point of fluorine-containing ether is At less than 200 DEG C, evaporative removal in the fluororesin film for forming fluorine-containing ether with composition from coated film formation easily by heating.
As the example of preferable fluorine-containing ether, 1,1,2,3,3,3- hexafluoro -1- (2,2,2- trifluoro ethoxy) can be exemplified Propane, 1,1,2,3,3,3- hexafluoros -1- (the fluorine propoxyl group of 2,2,3,3,3- five) propane, 1,1,2,3,3,3- hexafluoros -1- (2,2,3, 3- tetrafluoros propoxyl group) propane or 2,2,3,3,3- five fluoro- 1- (1,1,2,2- tetrafluoros ethyoxyl) propane.The manufacture of these fluorine-containing ethers Method is recorded in Japanese Unexamined Patent Publication 2002-201152 publications.
As the fluorine-containing ether with preferable boiling point, following compound can be exemplified.
C3F7OCH3、C4F9OCH3、C4F9OC2H5
These are by Sumitomo 3M Co., Ltd. with trade name NOVEC 7000, NOVEC 7100, NOVEC 7200, NOVEC 7300th, NOVEC 7500, NOVEC 7600 form are commercially available, can obtain.It can be used for the film formation composition of the present invention. It should be noted that NOVEC is trade mark.
As the commercially available fluorine-containing ether with preferable boiling point, Du Pont-Mitsui can be further exemplified Fluorochemicals Co., Ltd.s system, trade name Vertrel Suprion or Vertrel Sinera, can be obtained.
[fluorine-containing alcohol]
In order to further improve the dissolubility to fluororesin, the fluorine series solvent that film formation of the invention is included with composition removes Beyond above-mentioned fluorine-containing hydrocarbon system solvent or fluorine-containing ether, the fluorine-containing alcohol that following formulas (3) represent can also be contained.It is molten relative to fluorine system The gross mass of agent, preferably below 45 mass %, it is more preferably below 30 mass %.
R5-OH (3)
(in formula, R5For the alkyl of the ring-type of the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15, At least one of hydrogen atom in alkyl is replaced by fluorine atoms.)
On fluorine-containing alcohol, chemically set out in terms of excellent in stability, in aforementioned formula (3), preferably abutted with hydroxyl Carbon on unsubstituted have fluorine atom.
In the fluorine-containing alcohol that aforementioned formula (3) represents, R5For the straight-chain of carbon number 1~8, the branched of carbon number 3~10 or carbon Contained fluorine atom number easily applies for fluorine-containing alcohol more than number of hydrogen atoms number in the alkyl and alkyl of the ring-type of number 3~10 Cloth.
R5Methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, 1- can specifically be exemplified Amyl group, 2- amyl groups, 3- amyl groups, 1- hexyls, 2- hexyls, 3- hexyls, 1- heptyl, 2- heptyl, 3- heptyl, 1- octyl groups, 2- octyl groups, 3- Octyl group, cyclopenta, cyclohexyl, cyclopentyl-methyl or cyclohexyl methyl.At least one of hydrogen atom in these alkyl is by fluorine atom Substitution.
On fluorine-containing alcohol, from the aspect that the dissolubility to fluororesin is excellent, the chemical combination that preferably aforementioned formula (3) represents Fluorine atom number in thing is more than numbers of hydrogen atoms.
And then in the fluorine-containing alcohol of aforementioned formula (3) expression, the fluorine-containing alcohol of following formulas (7) or following formulas (8) expression exists It is chemically stable, it is more preferably used for the film formation composition of the present invention.
R8-CH2-OH (7)
(in formula, R8For the hydrofluorocarbons of the ring-type of the straight-chain of carbon number 1~7, the branched of carbon number 3~9 or carbon number 3~9 Base.)
(in formula, R9And R10It is each independently the straight-chain of carbon number 1~4, the branched of carbon number 3~6 or carbon number 3~6 The alkyl of ring-type, contained fluorine atom number is more than numbers of hydrogen atoms in alkyl.)
In formula (7), R8Can specifically exemplify methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, The tert-butyl group, 1- amyl groups, 2- amyl groups, 3- amyl groups, 1- hexyls, 2- hexyls, 3- hexyls, 1- heptyl, 2- heptyl, 3- heptyl, 2- octyl groups, 3- octyl groups, cyclopenta, cyclohexyl, at least one of hydrogen atom of cyclopentyl-methyl or cyclohexyl methyl are replaced by fluorine atoms and obtained The group arrived.It is preferred that fluorine atom number contained in these fluorine-containing alkyl is more than 2 more than numbers of hydrogen atoms.
In formula (8), R9And R10Material for the straight-chain of carbon number 1~3 is readily synthesized, and is preferable.R9And R10Specifically For can exemplify methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, 2- amyl groups, 3- amyl groups, 2- Hexyl, 3- hexyls, cyclopenta, cyclohexyl or cyclopentyl-methyl hydrogen atom at least one be replaced by fluorine atoms obtained from base , contained fluorine atom number is more than numbers of hydrogen atoms in these alkyl.
The boiling point of fluorine-containing alcohol is higher with substrate temperature during composition than coated film formation, preferably higher than coating temperature 20 DEG C with It is upper, further preferably high more than 50 DEG C.If the substrate temperature when boiling point of fluorine-containing alcohol is less than coated film formation composition, Fluorine-containing aliphatic alcohol rapidly volatilizees in painting work, and the fluororesin film formed can not obtain sufficient flatness.In addition, made The preferred boiling point of fluorine-containing alcohol is less than 200 DEG C, more preferably less than 180 DEG C.When the boiling point of fluorine-containing alcohol is higher than 200 DEG C, It is difficult to by heating evaporative removal in the fluororesin film for forming solvent from coated film formation composition.
In the fluorine series solvent that the film formation of the present invention is included with composition, the fluorine-containing alcohol in foregoing boiling spread Such as 1,1,1,3,3,3- hexafluoro -2- propyl alcohol, 2,2,2 tfifluoroethyl alcohol, 2,2,3,3- tetrafluoropropanols, 2,2,3,3 can be exemplified, The fluorine propyl alcohol of 3- five, 2,2,3,4,4,4- hexafluoros butanol, the fluoro butanols of 2,2,3,3,4,4,4- seven, 2,2,3,3,4,4,5,5- octafluoros penta Alcohol, the fluorine amylalcohols of 2,2,3,3,4,4,5,5,5- nine, the fluorine hexanols of 3,3,4,4,5,5,6,6,6- nine, 2,2,3,3,4,4,5,5,6,6, The difluoro enanthol of 7,7- ten, the trifluoro enanthol of 2,2,3,3,4,4,5,5,6,6,7,7,7- ten, 3,3,4,4,5,5,6,6,7,7,8,8, The trifluoro octanols of 8- ten, (1,2,2,3,3,4,4,5- octafluoros cyclopenta) methanol, (1,2,2,3,3,4,4,5- octafluoros cyclopenta) second Alcohol or 2- (1,2,2,3,3,4,4,5- octafluoro cyclopenta) propane -2- alcohol, can mix these solvents two or more use.
In these solvents, the film formation as the abundant dissolving present invention has with the fluororesin that composition includes without immersing The solvent of machine material, especially 2,2,2- trifluoroethanols, 2,2,3,3- tetrafluoropropanols, 2,2,3,4,4,4- hexafluoro butanol or 2,2,3, 3,4,4,5,5- octafluoropentanols are the film formation in the present invention with fluorine-containing alcohol used in composition, particularly preferred.
[other solvents]
In addition, in the fluorine series solvent that the film formation of the present invention is included with composition, as long as in the absence of to the molten of organic material The influence of solution or moistening, then it can also add for the purpose of the solubility of regulation viscosity, regulation boiling point and regulation fluororesin Add in addition to above-mentioned hydrofluorocarbons, fluorine-containing ether and fluorine-containing alcohol, not fluorine-containing alkane, ether, alcohol, ester, ketone or aromatic hydrocarbon etc..Phase For the gross mass of the solvent comprising fluorine series solvent, preferably below 20 mass %.
From the aspect close with the boiling point of foregoing fluorine series solvent, such as following solvent can be added.Alkane is preferred For the alkane of the straight-chain of carbon number 5~12, difference shape or ring-type, pentane, hexane, heptane, octane, nonyl can be specifically exemplified Alkane, decane, hendecane, dodecane, pentamethylene, hexamethylene, cycloheptane, methyl cyclopentane or hexahydrotoluene.Ketone is preferably carbon The ketone of number 5~12, it can specifically exemplify cyclopentanone, cyclohexanone, acetone, 2- butanone, 2 pentanone, propione, 3- methyl -2- Butanone, methyl-n-butyl ketone, 2- methyl -4- pentanones, 2-HEPTANONE or methyln-hexyl ketone.Ether is preferably the straight-chain of carbon number 4~16, difference shape or ring The ether of shape, such as Anaesthetie Ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ethers, diisobutyl ether, di-t-butyl can be exemplified Ether, diamyl ether, diisoamyl ether, hexyl ether, ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether or triethylene glycol Anaesthetie Ether.As alcohol, can be carbon number 1~ Substitution has what 1~3 hydroxyl formed on the alkyl of the ring-type of 10 straight-chain, the branched of carbon number 3~10 or carbon number 3~10 Alcohol, it can specifically exemplify methanol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- penta Alcohol, 2- amylalcohols, isoamyl alcohol, 4- methyl -2- amylalcohols, 1- hexanols, 2- hexanols, ethylene glycol, ethylene glycol single methyl ether, ethylene glycol list second Base ether, propane diols, propylene glycol monomethyl ether, propylene glycol monoethyl, diethylene glycol monomethyl ether or TC. As the ester of ester, preferably carbon number 1~12, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate can be specifically exemplified Ester, butyl acetate, isobutyl acetate, pentyl acetate, hexyl acetate, methyl lactate, ethyl lactate, methyl butyrate, ethyl butyrate, Propyl butyrate or propylene glycol monomethyl ether.As the aromatic hydrocarbon of aromatic hydrocarbon, preferably carbon number 6~12, specifically Benzene,toluene,xylene, ethylbenzene, trimethylbenzene, isopropylbenzene or diethylbenzene can be exemplified.
[the present invention film formation with the fluorine series solvent used in composition]
As the present invention film formation with the preferable fluorine series solvent used in composition, for example, as separate solvent, C can be exemplified4F9OCH3、C4F9OC2H5、CF3CF2CF2CF2CF2CH2CH2CH3, Vertrel Suprion or NOVEC 7300, As mixed solvent, can exemplify C4F9OCH3With 2,2,3,3,4,4,5,5- octafluoropentanols with mass ratio 100:0.01~70: 30 solvents mixed, by C4F9OCH3With 2,2,2 tfifluoroethyl alcohol with mass ratio 100:0.01~70:30 mix it is molten Agent, by C4F9OCH3With 2,2,3,4,4,4- hexafluoros butanol with mass ratio 100:0.01~70:30 solvents mixed, incite somebody to action C4F9OCH3With (1,2,2,3,3,4,4,5- octafluoros cyclopenta) ethanol with mass ratio 100:0.01~70:30 mix it is molten Agent, by C4F9OCH2CH3With 2,2,3,3- tetrafluoropropanols with mass ratio 100:0.01~70:30 solvents mixed, incite somebody to action CF3CF2CF2CF2CF2CH2CH2CH3With 2,2,2 tfifluoroethyl alcohol with mass ratio 100:0.01~70:30 solvents mixed, incite somebody to action CF3CF2CF2CF2CF2CH2CH2CH3With 2,2,3,3,4,4,5,5- octafluoropentanols with mass ratio 100:0.01~70:30 mixing and Into solvent, by CF3CF2CF2CF2CF2CH2CH2CH3With 2,2,3,4,4,4- hexafluoros butanol with mass ratio 100:0.01~70:30 The solvent that mixes, by Vertrel Suprion and 2,2,3,3,4,4,5,5- octafluoropentanol with mass ratio 100:0.01~ 70:30 solvents mixed, by NOVEC 7300 and the fluoro butanols of 2,2,3,3- tetra- with mass ratio 0.01~70:30 mix Solvent or by NOVEC 7300 and 2,2,3,3,4,4,5,5- octafluoropentanols with mass ratio 100:0.01~70:30 mixing and Into solvent.
3. film formation composition
[composition]
It is molten relative to fluorine system on the fluororesin and the ratio of components of fluorine series solvent contained by the film formation composition of the present invention The mass parts of agent 100, fluororesin be 0.1 mass parts more than and 25 mass parts below, be preferably 0.5 mass parts more than and 20 mass parts Below.When fluororesin is less than 0.1 mass parts, the fluororesin film of formation is thinning, and can not adequately protect organic semiconductor.Fluororesin is more When 25 mass parts, it is difficult to equably coating film forming.
The fluorine-containing rate of fluororesin contained by the film formation composition of the present invention for more than 30 mass % and 65 mass % with Under, and the fluorine-containing rate of preferably fluorine series solvent is more than 50 mass % and below 70 mass %.If fluorine-containing rate is in the range of being somebody's turn to do, Then it is readily soluble in fluorine series solvent.
The fluorine-containing rate of fluorine series solvent contained by the film formation composition of the present invention is more than 50 mass % and 70 mass % Below, more than 55 mass % and below 70 mass % are more preferably.During more than 70 mass %, foregoing fluororesin becomes to fill Divide dissolving.In addition, when being less than 50 mass %, when being coated with or printing on organic semiconductor film, the table of organic semiconductor film sometimes Face can dissolve or be swelled.
[additive]
, can be with the case where the degree as the organic matter for being coated with object will not be immersed in film the is formationed composition of the present invention Contain the composition in addition to above-mentioned fluororesin and solvent as additive.
For example, it can be compounded for the purpose of improving coating, levelability, film forming, storage stability or defoaming The additives such as surfactant.Specifically, the commodity of Dainippon Ink Chemicals as commercial surfactant can be included Name MEGAFAC, numbering F142D, F172, F173 or F183, trade name FLUORAD, the numbering FC- of Sumitomo 3M Co. Ltd. systems 135th, FC-170C, FC-430 or FC-431, the trade name SURFLON of AGC Seimi Chemical Co., Ltd.s, compile Number S-112, S-113, S-131, S-141 or S-145, or Dow Corning Toray Silicone Co., Ltd.s Trade name, SH-28PA, SH-190, SH-193, SZ-6032 or SF-8428.The compounding amount of these surfactants relative to The mass parts of resin 100 in resin combination are usually below 5 mass parts.It should be noted that MEGAFAC is DIC strain formula meetings The trade name of the fluorine system additive (surfactant surface modifier) of society, the fluorine that FLUORAD is Sumitomo 3M Co. Ltd. systems It is the trade name of surfactant, and the fluorine system surfactant that SURFLON is AGC Seimi Chemical Co., Ltd.s Trade name, carried out trade mark registration respectively.
Alternatively, it is also possible to be compounded curing agent.The curing agent used is not particularly limited, such as melamine can be exemplified Curing agent, urea resin curing agent, polynary acid as curing agent, isocyanate curing agent or epoxy hardener.Specifically, can illustrate Go out IPDI, hexamethylene diisocyanate, toluene di-isocyanate(TDI) or diphenylmethane diisocyanate The isocyanates such as ester and its isocyanuric acid ester, blocked isocyanate or biuret body etc., alkylated melamine, hydroxyl first The amino-compounds such as melmac or urea resin such as base melamine, imino group melamine are more by bisphenol-A etc. There is the epoxy hardener of more than 2 epoxy radicals obtained from the reaction of first phenol and epoxychloropropane.The compounding of these curing agent Amount is usually below 35 mass parts relative to the mass parts of resin 100 in resin combination.
4. organic semiconductor film
The organic semiconductor film being process to the film formation using the present invention with composition illustrates.As organic half The material of electrically conductive film, known material can be used.As organic semiconductor, pentacene, anthracene, aphthacene, phthalocyanine can be exemplified Deng the polyphenyl such as organic low molecular, polyacetylene system electroconductive polymer, polyparaphenylene and its derivative, polyphenylacetylene and its derivative Support is that the heterocycle system such as electroconductive polymer, polypyrrole and its derivative, polythiophene and its derivative, poly- Furan and its derivatives leads The electrical organic semiconductor such as macromolecule or Polyaniline and its derivative isoiony electroconductive polymer, organic charge movement network Compound.
Especially, in the organic semiconductor manufacture method of the present invention, it is preferably able to by using hydrocarbon system solvent or aromatic series The organic semiconducting materials that solvent removes as the Wet-type etching of etching solvent., can example as such organic semiconducting materials The organic low moleculars such as more cyclic condensation aromatic hydrocarbons such as anthracene, aphthacene and pentacene, phthalocyanine, polyacetylene system electric conductivity high score are shown Polyhenylene system electroconductive polymer, polypyrrole and its derivative such as sub, polyparaphenylene and its derivative, polyphenylacetylene and its derivative The heterocycle system such as thing, polythiophene and its derivative, poly- Furan and its derivatives electroconductive polymer.The organic semiconductor system of the present invention The method of making can be particularly preferably applied for more cyclic condensation aromatic hydrocarbons.
5. organic semi-conductor manufacture method
In the manufacture of the organic semiconductor device of the present invention, in order to by organic semiconductor film microfabrication into desired half Semiconductor film is protected during conductor circuit, fluororesin film is set on organic semiconductor film.
Formation for the organic semiconductor circuit in the manufacture of organic semiconductor device, it is also logical not using only photoetching process Cross and transferred pattern to using the print process of relief printing plate, intaglio plate, lithographic plate, silk-screen printing or stamped method etc. on fluororesin film, it is then right Organic semiconductor film is etched, and carries out pattern processing.
First, the pattern of the fluororesin film formed to the film formation using the present invention with composition on organic semiconductor adds Work illustrates.
The film formation of the present invention can be by carrying out wet type with composition on the organic semiconductor film being formed on substrate It is coated with and forms fluororesin film, pattern can be formed on fluororesin film by photoetching process, stamped method or print process.If Coating and carry out pattern processing on organic semiconductor film, then can be molten by subsequent use hydrocarbon system solvent or fragrant family The pattern is transferred on organic semiconductor film by the Wet-type etching of agent.In this way, by using the present invention, can be to organic semiconductor Film carries out microfabrication.
In addition, the film formation of the present invention can directly be formed on the organic material with composition by print process or ink-jet method Pattern, organic material can be transferred pattern to by the Wet-type etching of subsequent use hydrocarbon system solvent or fragrant family solvent On.By print process or ink-jet method directly when forming pattern on fluororesin film, film formation is used by the use of composition as ink. As print process, letterpress, intaglio printing, photogravure, offset printing, silk-screen printing, thermal transfer print can be exemplified Brush reverses hectographic printing.
, it is necessary to which in etching, fluororesin film is insoluble or is insoluble in etchant when fragrant family solvent is used as into etchant.Separately Outside, fluororesin film is stripped or remained from organic semiconductor circuit after the etching.During stripping, fluororesin film will not preferably make to have Machine semiconductor circuit deteriorates.When fluororesin film is remained in organic semiconductor film circuit, in order to not make organic semi-conductor circuit Short circuit occurs for pattern, is played a role preferably as dielectric film.
When carrying out pattern processing to organic semiconductor film, the film shape for forming the film for being used to protect organic semiconductor circuit Into with composition and its film, it is desirable to：(1) easily film formation is carried out on organic semiconductor film, (2) can not make organic semiconductor Circuit deteriorates and short circuit ground removes from organic semiconductor patterns, (3) have and the electrical characteristics of organic semiconductor circuit will not be produced The insulating properties of raw obstacle and (4) are difficult to be immersed easily by the fragrant family solvent as etchant.
Can basis in organic semi-conductor manufactures with the fluororesin film that composition is formed using the film formation of the present invention Need and dissolved and removed with specific fluorine series solvent.The solvent that can be used when being removed as dissolving, as long as to organic semiconductor Caused by influence it is small, then can use with the fluorine series solvent identical fluorine series solvent contained by film formation composition, can also be because The reason such as bigger to the dissolubility of fluororesin and use other fluorine series solvents.
The method removed as dissolving, can exemplify following method：By with the film formation group using the present invention Compound formed fluororesin film substrate be immersed in fluorine series solvent, make substrate vertical or inclined state under topple over fluorine system Solvent, while with spin coater make substrate rotation on one side topple over peel off solvent or by substrate be placed in peel off solvent saturation steaming In the chamber that atmosphere is enclosed.The quality of the fluorine series solvent used in dissolving removes is preferably 5 relative to the gross mass of fluororesin film More than times, it is more preferably more than 10 times.When the usage amount of fluorine series solvent is few, the removal of fluororesin film becomes insufficient.In addition, make The fluororesin film formed with the film formation composition of the present invention has insulating properties, therefore even if does not carry out dissolving removal and remaining The characteristic of semiconductor circuit will not be also damaged in the semiconductor element.
[one of the manufacture method of organic semiconductor device of the invention]
Using Fig. 1 to being specifically described using film formation with the organic semi-conductor manufacture method of composition, but use The film formation of the present invention is not limited to this with the organic semi-conductor manufacture method of composition.
First, as shown in Fig. 1 (A), on substrate 1, formed by being coated with or being deposited solutions of organic semiconductors by having The organic semiconductor film 2 that machine semiconductor film is formed.
Then, as shown in Fig. 1 (B), using the film formation composition of the present invention, formed on organic semiconductor film 2 Fluororesin film 3.
Film formation composition can be coated with dip-coating, spraying, spin coating, rod painting, applicator or roll coater etc., be coated with After the solvent-laden film of bag is made on organic semiconductor film 2, it is set to spontaneously dry and form fluororesin film 3.
It is then possible to which substrate 1 is heated, baking processing is carried out to fluororesin film 3.Heating-up temperature in baking is 250 DEG C Below.It it is more than 10 DEG C and 150 DEG C though preferred temperature also depends on the boiling point of solvent without being heated more than 250 DEG C Below.During less than 10 DEG C, drying needs for a long time, during higher than 150 DEG C, the uniformity on the surface of the fluororesin film 3 formed sometimes It is impaired.In addition, the heat time is more than 30 seconds and less than 15 minutes.When being shorter than 30 seconds, worry have solvent residual in fluororesin film 3 Stay, without extending to more than 15 minutes.
Then, as shown in Fig. 1 (C), photoetching or impressing, letterpress, intaglio printing, photogravure, flat are utilized Plate printing, silk-screen printing, thermal transfer printing reverse the print processes or ink-jet method etc. such as hectographic printing, and fluororesin film 3 is carried out Pattern is processed.
Using photoetching, by the present invention film formed the fluororesin film 3 formed with composition pattern process in, at this The upper strata of fluororesin film forms photoresist film (not shown).For example, can be by using the molten of fluororesin film 3 will not be immersed Agent carrys out painting photoresist or attaches the method for dry film photoresist to form photoresist film.Formed by coating photic During resist film, preferably use will not immerse the hydrocarbon system solvent and fragrant family solvent of fluororesin film 3.Then, across photomask Photoresist film is exposed, carry out pattern processing, by using the Wet-type etching of solvent, reactive ion etching or Gas etch carries out pattern processing to fluororesin film 3.
In using the processing of the pattern of the fluororesin film 3 of print process, pattern is transferred to fluororesin film 3 from printing original edition plate On.The method of transfer can exemplify：The bumps of printing original edition plate are pressed on into the method for fluororesin film 3, only by the convex of printing original edition plate The method that portion presses on fluororesin film 3 and removes fluororesin film 3.It is preferably logical when pattern is transferred from printing original edition plate to fluororesin film 3 Crossing heating or the swelling of solvent makes fluororesin film 3 that softening occur and easily produce change in shape.
In using the processing of the pattern of the fluororesin film 3 of ink-jet method, it is desirable that the position for remaining fluororesin film 3 passes through ink-jet Material of the coating with etching patience, the fluororesin film 3 at uncoated position is subjected to pattern processing by etching.As pattern The method of processing, Wet-type etching, reactive ion etching or gas etch using solvent can be exemplified.
At this time it is also possible to substrate 1 be heated and the fluororesin film 3 to being processed through pattern carries out baking processing.In baking Heating-up temperature is less than 250 DEG C.More than 250 DEG C need not be heated to, though preferred temperature also depends on the boiling point of solvent, is More than 10 DEG C and less than 150 DEG C.During less than 10 DEG C, drying needs for a long time, during higher than 150 DEG C, the fluororesin film 3 that is formed sometimes The uniformity on surface be damaged.In addition, the heat time is more than 30 seconds and less than 15 minutes.When being shorter than 30 seconds, fluororesin is worried There is dissolvent residual in film 3, without extending to more than 15 minutes.Fluororesin film 3 through pattern processing is to organic semiconductor film layer 2 Wet-type etching process in protection to carry out pattern processing position organic semiconductor film 2.
Then, as shown in Fig. 1 (D), pattern 2b is formed in organic semiconductor film layer 2 by Wet-type etching.It is specific and Speech, by the way that substrate 1 and organic semiconductor film 2 and the fluororesin film 3 processed through pattern are immersed in into hydrocarbon system solvent or fragrance In family solvent or the methods of toppling over hydrocarbon system solvent or fragrant family solvent, the fluororesin film 3 that will not processed through pattern The dissolving of organic semiconductor film 2 at coated position removes.Thus, the pattern for being formed at fluororesin film 3 is transferred to and organic partly led On body film 2, pattern 2b is obtained.
And then as shown in Fig. 1 (E), fluororesin film 3 can be dissolved into removal using fluorine series solvent.It is molten as what is used Agent, such as the fluorine series solvent identical solvent included with film formation with composition can be used., can example as dissolving minimizing technology Show：The method that substrate 1 is immersed in fluorine series solvent, make substrate vertical or inclined state under topple over fluorine series solvent Method, while with spin coater make substrate 1 rotation while toppling over the method for fluorine series solvent or substrate 1 being placed in fluorine series solvent Saturated vapor atmosphere chamber in method.Fluororesin film 3 can also play a role as interlayer dielectric.
6. the cleaning method of device
The fluororesin being included in form fluororesin film in film formation composition is molten in ketone, ether and carboxylate Solution, therefore the cleaning of the apparatus for coating of the formation for fluororesin film 3 can be carried out by using these organic solvents.Cleaning Method is determined by environment residing for the shape of device, device etc., can exemplify device being immersed in cleaning organic solvent In, to device spray clean organic solvent and it is flowed or the methods of to wiping after device spray clean organic solvent.
7. the feature of the present invention
As described above, the present invention film formation composition be characterised by, using will not make organic material dissolve, swelling Deng specific fluorine series solvent, and containing being dissolved in fluororesin therein.
The present invention film formation with composition when being coated with organic semiconductor film, will not make organic semiconductor film dissolve or It is swelled and immerses, therefore wet type film forming can be carried out on organic semiconductor film and form film.And the fluororesin film is being used up , can not be by hydrocarbon system solvent when lithography, printing or impressing carry out pattern processing, then carry out Wet-type etching to organic semiconductor film Or the etchant such as fragrant family solvent immerses ground and carries out pattern processing to organic semiconductor film.Used in addition, the film of the present invention is formed Fluorine series solvent contained by composition will not make organic semiconductor film dissolve or be swelled and soak when being coated with organic semiconductor film Enter, the wet of fluororesin film can be carried out on the organic material.And the film is using photoetching process, printing, such as stamped method When carrying out pattern processing, carrying out Wet-type etching to organic semiconductor film, it can not be lost by hydrocarbon system solvent or fragrant family solvent etc. Carve agent and immerse ground to organic semiconductor film progress pattern processing.So, can if using film formation composition of the invention Enough organic semiconductor films on substrate carry out microfabrication, circuit pattern are made, and can be suitably used for organic semiconductor member The manufacture of part.
And then the fluororesin that film formation of the invention is included with composition has appropriate glass transition temperature, is easy to Process, be easy to film forming, there is high-fire resistance, therefore can suitably be used as the interlayer dielectric of organic semiconductor device.
Embodiment
The present invention is illustrated by the following examples, but the present invention is not limited by following examples.
[synthesis of fluororesin]
In an embodiment of the present invention, as long as no the special synthesis recorded, then fluororesin is carried out by following method.
As reaction vessel, capacity 50mL glass system eggplant type flask is used.The third of ormal weight is weighed in reaction vessel Olefin(e) acid ester derivant and double (the 2- methyl-props of the 2- butanone as polymer solvent and the dimethyl 2,2- azos as initiator Acid esters) (name of an article, V-601, Wako Pure Chemical Industries, Ltd.'s system), condenser pipe is installed, while stirring with nitrogen in reaction vessel Enter line replacement.Then, connect reaction vessel with the oil bath of temperature adjustment to 80 DEG C together to heat 6 hours.After heating terminates, with rotation Reaction solution is concentrated into 1.5 times of used monomer gross mass by evaporator, by obtained concentrate and the monomer for reacting The heptane mixing of 15 times of amounts of gross mass, obtains sediment, is collected by filtering.Sediment is being utilized into the dry of oil pump decompression 65 DEG C are heated in dry machine to be dried, and obtain fluororesin.
For obtained fluororesin, measure gel permeation chromatography (GPC), weight average molecular weight Mw and molecular weight dispersion are calculated Mw/Mn (value calculated with weight average molecular weight Mw divided by number average molecular mass Mn).GPC uses TOSOH Co., Ltd's system, machine Name HLC-8320, will be similarly chromatographic column (name of an article, the TSKgel GMH of TOSOH Co., LtdXL) 3 pieces series connection, use tetrahydrochysene furan Mutter and determined as developing solvent, detector using refringence detector.Oil repellent in obtained fluororesin is by passing through core The NMR spectrum for the core of fluorine 19 that magnetic resonance device (model JNM-ECA400, Jeol Ltd.'s system) measures calculates. Specifically, fluororesin 25mg~35mg is weighed with being used as interior target Isosorbide-5-Nitrae-bis- (trifluoromethyls) benzene 5mg~10mg, makes its dissolving In deuterated acetone 0.5g, by the NMR spectrum of the core of fluorine 19 measured to the solution from acrylate derivative Peak intensity and the content that the repeat unit from acrylate derivative is scaled from the ratio between interior target peak intensity.
[fluororesin synthesis example 1]
Methacrylic acid 2,2,3,3- tetrafluoro propyl ester 5.00g (25.0mmol), 2- butanone are taken in reaction vessel 10.0g and initiator 0.575g (2.50mmol), radical polymerization is carried out with the method described in above-mentioned [synthesis of fluororesin] Close.As a result, obtain the fluororesin 1 that 4.90g includes the repeat unit that following formula (9) represents.With the quality of the monomer used On the basis of yield be 98 mass %.Weight average molecular weight Mw is 11,000, molecular weight dispersion Mw/Mn is 1.34.Fluorine in resin Content is 38 mass %.
[fluororesin synthesis example 2]
Methacrylic acid 2,2,3,3,4,4,5,5- octafluoro pentyl ester 5.00g (16.7mmol), 2- are taken in reaction vessel Butanone 10.0g and initiator 0.384g (1.67mmol), carried out freely with the method described in above-mentioned [synthesis of fluororesin] Base polymerize.As a result, obtain the fluororesin 2 that 4.00g includes the repeat unit that formula (10) represents.Using the quality of monomer that uses as The yield of benchmark is 80 mass %.Weight average molecular weight Mw is 15,000, molecular weight dispersion Mw/Mn is 1.67.Fluorine in resin contains Measure as 51 mass %.
[fluororesin synthesis example 3]
The difluoro heptyl ester 5.00g of methacrylic acid 2,2,3,3,4,4,5,5,6,6,7,7- ten are taken in reaction vessel (12.5mmol), 2- butanone 10.0g and initiator 0.288g (1.25mmol), described in above-mentioned [synthesis of fluororesin] Method carry out radical polymerization.As a result, obtain the fluororesin 3 that 3.65g includes the repeat unit that following formula (11) represents. Yield on the basis of the quality of the monomer used is 73 mass %.Weight average molecular weight Mw is 13,000, molecular weight dispersion Mw/Mn For 1.49.Oil repellent in resin is 57 mass %.
[fluororesin synthesis example 4]
The fluorine propyl ester 5.00g (22.9mmol) of methacrylic acid 2,2,3,3,3- five, 2- butanone are taken in reaction vessel 10.0g, initiator 0.528g (2.29mmol), radical polymerization is carried out with the method described in above-mentioned [synthesis of fluororesin]. As a result, obtain the fluororesin 4 that 2.70g includes the repeat unit that following formula (12) represents.Using the quality of monomer that uses as The yield of benchmark is 54 mass %.Weight average molecular weight Mw is 9,500, molecular weight dispersion Mw/Mn is 1.48.Oil repellent in resin For 44 mass %.
[fluororesin synthesis example 5]
The fluorine butyl ester 5.00g (18.6mmol) of methacrylic acid 2,2,3,3,4,4,4- seven, 2- fourths are taken in reaction vessel Ketone 10.0g and initiator 0.429g (1.86mmol), free radical is carried out with the method described in above-mentioned [synthesis of fluororesin] Polymerization.As a result, obtain the fluororesin 5 that 3.40g includes the repeat unit that following formula (13) represents.With the matter of the monomer used Yield on the basis of amount is 68 mass %.Weight average molecular weight Mw is 11,000, molecular weight dispersion Mw/Mn is 1.35.In resin Oil repellent is 50 mass %.
[fluororesin synthesis example 6]
Taken in reaction vessel the fluorine pentyl ester 5.00g (15.7mmol) of methacrylic acid 2,2,3,3,4,4,5,5,5- nine, 2- butanone 10.0g and initiator 0.362g (1.57mmol), carried out certainly with the method described in above-mentioned [synthesis of fluororesin] It is polymerize by base.As a result, obtain the fluororesin 6 that 3.20g includes the repeat unit that following formula (14) represents.With the monomer used Quality on the basis of yield be 64 mass %.Weight average molecular weight Mw is 6,400, molecular weight dispersion Mw/Mn is 1.32.In resin Oil repellent be 54 mass %.
[fluororesin synthesis example 7]
Taken in reaction vessel the own ester 5.00g (15.1mmol) of the fluorine of methacrylic acid 3,3,4,4,5,5,6,6,6- nine, 2- butanone 10.0g and initiator 0.347g (1.51mmol), carried out certainly with the method described in above-mentioned [synthesis of fluororesin] It is polymerize by base.As a result, obtain the fluororesin 7 that 3.25g includes the repeat unit that following formula (15) represents.With the monomer used Quality on the basis of yield be 65 mass %.Weight average molecular weight Mw is 13,000, molecular weight dispersion Mw/Mn is 1.49.Resin In Oil repellent be 52 mass %.
[fluororesin synthesis example 8]
The trifluoro monooctyl ester 5.00g of methacrylic acid 3,3,4,4,5,5,6,6,7,7,8,8,8- ten are taken in reaction vessel (11.7mmol), 2- butanone 10.0g, initiator 0.266g (1.17mmol), with the side described in above-mentioned [synthesis of fluororesin] Method carries out radical polymerization.As a result, obtain the fluororesin 8 that 3.30g includes the repeat unit that following formula (16) represents.So that Yield on the basis of the quality of monomer is 66 mass %.Weight average molecular weight Mw is 4,900, molecular weight dispersion Mw/Mn is 1.13.Oil repellent in resin is 57 mass %.
[fluororesin synthesis example 9]
Methacrylic acid 1,1,1,3,3,3- hexafluoro isopropyl ester 5.00g (21.2mmol), 2- fourths are taken in reaction vessel Ketone 10.0g and initiator 0.488g (2.12mmol), free radical is carried out with the method described in above-mentioned [synthesis of fluororesin] Polymerization.As a result, obtain the fluororesin 9 that 1.70g includes the repeat unit that following formula (17) represents.With the matter of the monomer used Yield on the basis of amount is 34 mass %.Weight average molecular weight Mw is 5,000, molecular weight dispersion Mw/Mn is 1.64.Fluorine in resin Content is 48 mass %.
[fluororesin synthesis example 10]
Acrylic acid 1,1,1,3,3,3- hexafluoro isopropyl ester 10.00g (45.0mmol), 2- butanone are taken in reaction vessel 10.0g and initiator 1.037g (4.50mmol), radical polymerization is carried out with the method described in above-mentioned [synthesis of fluororesin] Close.As a result, obtain the fluororesin 10 that 9.00g includes the repeat unit that following formula (18) represents.With the matter of the monomer used Yield on the basis of amount is 90 mass %.Weight average molecular weight Mw is 29,000, molecular weight dispersion Mw/Mn is 3.00.In resin Oil repellent is 51 mass %.
[fluororesin synthesis example 11]
Methacrylic acid 1,1,1,3,3,3- hexafluoro isopropyl ester 5.15g (21.8mmol), propylene are taken in reaction vessel Sour 1,1,1,3,3,3- hexafluoros isopropyl ester 4.85g (21.8mmol), 2- butanone 10.0g and initiator 0.804g (3.49mmol), radical polymerization is carried out with the method described in above-mentioned [synthesis of fluororesin].As a result, obtain 9.30g bags The fluororesin 11 of the repeat unit represented containing following formula (19).Yield on the basis of the quality of the monomer used is 93 matter Measure %.Weight average molecular weight Mw is 5,400, molecular weight dispersion Mw/Mn is 1.86.Oil repellent in resin is 50 mass %.
[fluororesin synthesis example 12]
Methacrylic acid 1,1,1,3,3,3- hexafluoro isopropyl ester 3.97g (16.8mmol), methyl are taken in reaction vessel Butyl acrylate 1.03g (7.24mmol), 2- butanone 10.0g and initiator 0.111g (0.482mmol), with above-mentioned [fluorine tree The synthesis of fat] described in method carry out radical polymerization.As a result, obtaining 3.47g includes the weight that following formula (20) represents The fluororesin 12 of multiple unit.Yield on the basis of the quality of the monomer used is 69 mass %.Weight average molecular weight Mw is 6, 600th, molecular weight dispersion Mw/Mn is 1.47.Oil repellent in resin is 38 mass %.
[fluororesin synthesis example 13]
Methacrylic acid 1,1,1,3,3,3- hexafluoro isopropyl ester 3.88g (16.4mmol), methyl are taken in reaction vessel Acrylic acid 2- ethoxy ethyl esters 1.12g (7.08mmol), 2- butanone 10.0g and initiator 0.115g (0.499mmol), use Method described in above-mentioned [synthesis of fluororesin] carries out radical polymerization.As a result, obtaining 3.91g includes following formula (21) The fluororesin 13 of the repeat unit of expression.Yield on the basis of the quality of the monomer used is 78 mass %.Weight average molecular weight Mw is 16,000, molecular weight dispersion Mw/Mn is 1.65.Oil repellent in resin is 38 mass %.
[being used for the resins synthesis example 1 compared]
N-BMA 5.00g (35.2mmol), 2- butanone 10.00g are taken in reaction vessel and is triggered Agent 0.162g (0.704mmol), radical polymerization is carried out with the method described in above-mentioned [synthesis of fluororesin].As a result, The resin 14 for the repeat unit that following formula (22) represents is included to 0.88g.Weight average molecular weight Mw is 16,000, molecular weight dispersion Mw/Mn is 1.48.Yield on the basis of the quality of the monomer used is 18 mass %.
[being used for the resins synthesis example 2 compared]
Taken in reaction vessel methacrylic acid -2- ethoxy ethyl esters 10.00g (63.2mmol), 2- butanone 10.00g, And initiator 0.225g (0.977mmol), carry out radical polymerization with the method described in above-mentioned [synthesis of fluororesin].Its As a result, the resin 15 that 6.21g includes the repeat unit that following formula (23) represents is obtained.Weight average molecular weight Mw is 8,000, molecule The scattered Mw/Mn of amount is 1.45.Yield on the basis of the quality of the monomer used is 62 mass %.
[dissolubility evaluation of the fluororesin in fluorine series solvent]
For foregoing fluororesin 1~13, for resin 14 of the comparative example without fluorine atom and resin 15 and by Poly- (methyl methacrylate) (the hereinafter sometimes referred to PMMA that Sigma-Aldrich Japan K.K. are bought.Polystyrene changes Calculate weight average molecular weight 15,000), evaluate the dissolubility in fluorine series solvent.
<Evaluation method>
Added into each solvent and be 10 mass % as the fluororesin of solute, mixed at room temperature, visually to confirm It is to dissolve and separate out and suspend without solid or have solid to separate out and suspend, have insoluble composition.
<Evaluation result>
Evaluation result is shown in table 4~19.The fluororesin 1~13 that 4~table of table 16 shows to belong to scope is various Dissolubility evaluation in fluorine series solvent.Table 17 shows that the dissolubility evaluation of the resin 14 without fluorine atom for comparing (is compared Example 1~4).Table 18 shows dissolubility evaluation (comparative example 5~8) and the table 19 of the resin 15 without fluorine atom for comparing PMMA dissolubility evaluation (comparative example 9~11) is shown.
As shown in table 4~16, fluororesin 1~13 is dissolved in the fluorine series solvent described in table 4~16.On the other hand, such as table 17 Shown in~18, for the resin 14 without fluorine atom insoluble in the fluorine series solvent described in table 17, the resin 15 without fluorine atom is insoluble In the fluorine series solvent described in table 18.PMMA is insoluble in the fluorine series solvent described in table 19.It should be noted that in table NOVEC is that the trade name of the hydrofluoroether (HFE) of Sumitomo 3M Co. Ltd. systems, Vertrel Suprion are Du Pont-Mitsui The trade name of Fluorochemicals Co., Ltd.s, NOVEC and Vertrel have carried out trade mark registration.
[table 4]
The dissolubility evaluation of fluororesin 1
Solute Solvent Evaluation
Embodiment 1 C4H9OCH3With 2,2,2 tfifluoroethyl alcohol with mass ratio 7:3 mixing Dissolving
[table 5]
The dissolubility evaluation of fluororesin 2
Solvent Evaluation
Embodiment 2 CF3CF2CF2CF2CF2CH2CH2CH3 Dissolving
[table 6]
The dissolubility evaluation of fluororesin 3
[table 7]
The dissolubility evaluation of fluororesin 4
[table 8]
The dissolubility evaluation of fluororesin 5
[table 9]
The dissolubility evaluation of fluororesin 6
[table 10]
The dissolubility evaluation of fluororesin 7
[table 11]
The dissolubility evaluation of fluororesin 8
[table 12]
The dissolubility evaluation of fluororesin 9
[table 13]
The dissolubility evaluation of fluororesin 10
[table 14]
The dissolubility evaluation of fluororesin 11
[table 15]
The dissolubility evaluation of fluororesin 12
[table 16]
The dissolubility evaluation of fluororesin 13
[table 17]
For the dissolubility evaluation of the resin 14 compared
[table 18]
For the dissolubility evaluation of the resin 15 compared
[table 19]
PMMA dissolubility evaluation
[the cleaning evaluation of fluororesin film]
<Evaluation method>
For comprising the fluororesin 1~13 obtained in synthesis example 1~13 and the fluororesin film of solvent, as not fluorine-containing clear Wash and use solvent, using this 3 kinds of 2- butanone, propylene glycol monomethyl ether and ethyl acetate, carry out cleaning evaluation (embodiment 60~72).As the solvent of film formation composition, using NOVEC 7300 and Vertrel Suprion and 2,2,3,3,4, 4,5,5- octafluoropentanols are with mass ratio 2:2:1 solvent mixed.Film formation is set to 10 matter with the resin concentration of composition Measure %.
As specific evaluation method, each film comprising fluororesin 1~13 is formed into composition coating on a silicon substrate Fluororesin film is formed, is then immersed in cleaning solvent, is taken out after 30 seconds, its drying is made by air-blowing, utilizes optical interference coating Thick instrument (Sentech Instrucments, Germany system, machine name FTP500) is remembered if having evaluated whether residual film, without residual film To be capable of washing.
<Evaluation result>
Evaluation result is shown in table 20.As shown in table 20, fluororesin 1~13 is all without residual film, can with 3 kinds it is not fluorine-containing Solvent for cleaning cleans.
[table 20]
The cleaning evaluation of film
PGMEA：Propylene glycol monomethyl ether
[fluororesin is evaluated the patience of Wet-type etching solvent]
<Evaluation method>
To the fluororesin film comprising fluororesin 1~13 and the resin 14,15 and PMMA without fluorine atom for comparing The patience to Wet-type etching solvent evaluate.Specifically, in silicon substrate, (diameter 10cm, surface are formed with autoxidation Film) on be respectively coated film formation composition of the invention comprising fluororesin 1~13 and for comparing without fluorine atom Resin 14,15 and PMMA, the fluororesin film of formation is impregnated 5 minutes in Wet-type etching solvent together with substrate, if leaching Thickness after stain is more than 30% of the thickness before dipping, then is judged as there is patience.
Fluororesin film is formed on a silicon substrate to carry out by the following method：By the combination preparation by fluororesin and fluorine series solvent Film of the invention formed with the coating of composition (the mass % of concentration 3) spin-coating method on a silicon substrate, then in 130 DEG C of hot plate On make its heat drying 3 minutes.As solvent, using by C4F9OCH2CH3With Vertrel Suprion and 2,2,3,3,4,4, 5,5- octafluoropentanols are with mass ratio 4:4:2 solvents mixed.The film for forming not fluorine-containing resin on a silicon substrate passes through such as Lower method is carried out：The film formation prepared using butyl acetate as solvent is used into spin-coating method with composition (the mass % of resin concentration 3) Coating on a silicon substrate, then makes its heat drying 3 minutes on 130 DEG C of hot plate.The thickness of fluororesin film is done using optics Film thickness gauge (Sentech Instrucments, Germany system, machine name FTP500) is related to determine.So that the thickness of fluororesin film The mode spent for more than 150nm and below 300nm adjusts solution concentration and spincoating conditions.As Wet-type etching solvent, benzene is used With this 3 kinds of toluene and dimethylbenzene.
<Evaluation result>
The result of evaluation, the fluororesin film comprising fluororesin 1~13 all have patience to foregoing 3 kinds of Wet-type etching solvents. On the other hand, there is no patience comprising the film for comparing resin 14,15 without fluorine atom and PMMA.
[the insulating properties evaluation of film]
<Evaluation method>
Evaluate the electrical insulating property of fluororesin 1~13.Specifically, it is on metal substrate (diameter 7.5cm, SUS316 system) It is coated with the film formation composition of the present invention and is formed, the fluororesin film surface comprising fluororesin 1~13 is made by sputtering Gold electrode (diameter 4cm circle), applies voltage between substrate and electrode, evaluates whether to cause insulation breakdown.
Fluororesin film is formed on metallic substrates to carry out by the following method：By by fluororesin 1~13 and fluorine series solvent Film of the invention prepared by combination is formed with the coating of composition (the mass % of concentration 3) spin-coating method on a silicon substrate, then 130 DEG C hot plate on make its heat drying 3 minutes.As solvent, using by C4F9OCH2CH3With Vertrel Suprion and 2,2, 3,3,4,4,5,5- octafluoropentanols are with mass ratio 4:4:2 solvents mixed.So that the thickness of fluororesin film is more than 150nm And the concentration and spincoating conditions of below 300nm mode adjusting film formation composition.Test voltage is with as 1.5kV/mm Mode based on fluororesin film thickness setting.
<Evaluation result>
The result of evaluation, whole fluororesin do not observe the insulation breakdown under test voltage, and display has insulating properties.
[coating of film formation composition of the invention on organic semiconductor film]
<Evaluation method>
Evaluate coating of the fluororesin 1~13 on organic semiconductor film.As shown in figure 1, in diameter 10cm silicon substrate Upper formation organic semiconductor film 2, fluororesin film 3 is formed on organic semiconductor film 2 using the film formation of the present invention with composition. Then with observation by light microscope substrate, section.If being able to confirm that organic semiconductor film 2 forms layer with fluororesin film 3, Can coating be coated with well.Material for forming organic semiconductor film 2, as dissolving in the organic of aromatic hydrocarbon solvents The example of semi-conducting material, use the anthracene for the Ppolynuclear aromatic hydrocarbon for belonging to organic low molecular.
Specifically, the formation of organic semiconductor film 2 by prepare the mass % of concentration 0.10 anthracene toluene solution and It is cast on silicon substrate, it is dried and is carried out at room temperature, obtains the anthracene film as organic semiconductor film 2 that thickness is 100nm 2.The formation of fluororesin film 3 is carried out by the following method：Using fluororesin 1~4, the NOVEC of fluorine series solvent is served as 7300 with the mass ratioes 7 of 2,2,3,3,4,4,5,5- octafluoropentanols:3 mixed solvent is adjusted to the mass % of concentration 3, is foring It is coated, is dried at room temperature for 10 minutes using spin-coating method on the silicon substrate of above-mentioned anthracene film 2.
<Evaluation result>
The result of evaluation, the fluororesin film 3 of the fluororesin 1~13 of formation all confirm anthracene film 2 and formed with fluororesin film 3 Layer, can be coated with.
[utilizing the protection of the organic semiconductor film of the fluororesin film of the present invention]
<Evaluation method>
Whether the fluororesin film 3 of evaluation fluororesin 1~13 can remove from the anthracene film 2 as organic semiconductor film 2.It is right In the material for forming organic semiconductor film 2, as the example for the organic semiconducting materials for dissolving in aromatic hydrocarbon solvents, work is used For the anthracene of the Ppolynuclear aromatic hydrocarbon of organic low molecular.
Specifically, anthracene film 2 is formed on foregoing silicon substrate plate, is formed thereon using the film formation of the present invention with composition Fluororesin film 3.The fluororesin film 3 for so making anthracene film 2 and the film formation composition using the present invention is laminated obtained silicon substrate Plate impregnates 30 seconds in toluene.Then the silicon substrate is impregnated 60 seconds in the fluorine series solvent for removing fluororesin film 3 for dissolving. Fluororesin film 3 using fluorine series solvent dissolving remove after, if anthracene film 2 on silicon substrate be present and its thickness without more than 10% change Change, be then judged as that anthracene film 2 is protected from toluene influence by fluororesin film 3 and fluorine series solvent can not influence organic semiconductor film Ground removes fluororesin film 3.
The formation of fluororesin film 3 is carried out as follows：Using fluororesin 1~13, the NOVEC of fluorine series solvent is served as 7300 with the mass ratioes 7 of 2,2,3,3,4,4,5,5- octafluoropentanols:3 mixed solvent is adjusted to the mass % of concentration 3, is foring It is coated, is dried at room temperature for 10 minutes using spin-coating method on the silicon substrate of above-mentioned anthracene film.
<Evaluation result>
When the dissolving of fluororesin film 3 of the toluene dipping after 30 seconds uses the NOVEC 7200 as fluorine series solvent in removing, The thickness of whole anthracene films 2 without more than 10% change, can carry out the protection of anthracene film 2 and the stripping of fluororesin film 3.
Description of reference numerals
1 substrate
2 organic semiconductor films or anthracene film
3 fluororesin films
2b patterns

Claims (19)

1. a kind of film formation composition, it is the film formation combination for forming fluororesin film on organic semiconductor film Thing, it is included：The fluororesin and fluorine series solvent of the repeat unit represented containing formula (1),
As fluororesin, containing the fluororesin that fluorine-containing rate is more than 30 mass % and below 65 mass %,
Fluorine series solvent contains hydrofluorocarbons or fluorine-containing ether,
Hydrofluorocarbons are the straight-chain of carbon number 4~8, the hydrocarbon of branched or ring-type, and at least one of the hydrogen atom in hydrocarbon is taken by fluorine atom Generation,
Fluorine-containing ether is the fluorine-containing ether that formula (2) represents,
In formula (1), R1It is each independently hydrogen atom, fluorine atom, methyl or trifluoromethyl, R2It is each independently carbon number 1~15 Straight-chain, the fluorine-containing alkyl of the ring-type of the branched of carbon number 3~15 or carbon number 3~15, the hydrogen atom in alkyl can be by fluorine Atom substitutes, and at least one fluorine atom is included in repeat unit；
R3-O-R4 (2)
In formula (2), R3And R4It is each independently the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15 The alkyl of ring-type, at least one of the hydrogen atom in compound are replaced by fluorine atoms.
2. film formation composition according to claim 1, wherein, fluorine series solvent also represents fluorine-containing containing formula (3) Alcohol,
R5-OH (3)
In formula (3), R5For the alkyl of the ring-type of the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15, hydrocarbon At least one of hydrogen atom in base is replaced by fluorine atoms.
3. film formation composition according to claim 1, it is more than 50 mass % and 80 mass % that it, which contains fluorine-containing rate, Following fluorine series solvent is as fluorine series solvent.
4. a kind of fluororesin film, it is to be coated with the film formation any one of 1~claim 3 of claim with composition Formed on organic semiconductor film.
5. a kind of manufacture method of organic semiconductor device, it includes following process：
Film formation any one of 1~claim 3 of claim is coated on shape on organic semiconductor film with composition Process into fluororesin film, the process that pattern processing is carried out to the fluororesin film and organic semiconductor film is entered by etching The process of row pattern processing.
6. manufacture method according to claim 5, wherein, use light in the process for carrying out pattern processing to fluororesin film Lithography.
7. manufacture method according to claim 5, wherein, using print in the process that pattern processing is carried out to fluororesin film Brush method.
8. manufacture method according to claim 5, wherein, using pressure in the process that pattern processing is carried out to fluororesin film Print method.
9. manufacture method according to claim 5, wherein, by etching the work to organic semiconductor film progress pattern processing Sequence is to carry out the work of pattern processing to organic semiconductor film by using the Wet-type etching of hydrocarbon system solvent or fragrant family solvent Sequence.
10. manufacture method according to claim 9, wherein, fragrant family solvent is benzene, toluene or dimethylbenzene.
11. manufacture method according to claim 5, it includes the process for removing fluororesin film.
12. manufacture method according to claim 11, wherein, the process that fluororesin film is removed is film is dissolved into fluorine system Process in solvent.
13. manufacture method according to claim 12, wherein, the fluorine series solvent used in the process that fluororesin film is removed Contain hydrofluorocarbons or fluorine-containing ether.
14. manufacture method according to claim 13, wherein, the fluorine series solvent used in the process that fluororesin film is removed What the straight-chain, branched containing carbon number 4~8 or at least one of the hydrogen atom in the hydrocarbon and hydrocarbon of ring-type were replaced by fluorine atoms contains Fluorohydrocarbon is as hydrofluorocarbons.
15. manufacture method according to claim 13, wherein, the fluorine series solvent used in the process that fluororesin film is removed Contain the fluorine-containing ether of formula (2) expression as fluorine-containing ether,
R3-O-R4 (2)
In formula (2), R3And R4It is each independently the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15 The alkyl of ring-type, at least one of the hydrogen atom in compound are replaced by fluorine atoms.
16. manufacture method according to claim 12, wherein, the fluorine series solvent used in the process that fluororesin film is removed The fluorine-containing alcohol also represented containing formula (3),
R5-OH (3)
In formula, R5For the alkyl of the ring-type of the straight-chain of carbon number 1~15, the branched of carbon number 3~15 or carbon number 3~15, in alkyl At least one of hydrogen atom be replaced by fluorine atoms.
17. a kind of organic semiconductor device, it is the manufacture method any one of by 5~claim 16 of claim Manufacture.
18. a kind of display of organic electroluminescence, it use the organic semiconductor device described in claim 17.
19. a kind of liquid crystal display, it use the organic semiconductor device described in claim 17.
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